Process for obtaining reserves under azo-dyestuffs



Patented Aug. 8, 1933 PRQCESS FOR QBTAINING RESERVES UNDER AZO-DYESTUFFSRobert I-laller, Riehen, near Basel, Switzerland, assignor to Society ofChemical Industry in Basle, Basel, Switzerland No Drawing. ApplicationJuly 7, 1932, Serial 'No. 621,310, and in Switzerland July 23, 1931 8Claims.

The present invention relates to the production of white and coloredreserves under such azo-dyestuffs which are obtained by treating fibersimpregnated with coupling components'with diazocompounds.

It has been found that the property of the nor that the salts of thexanthogenic acid are printed on the untreated goods, then treating thegoods with a coupling component, and, after drying, effecting thedevelopment in'a bath of the diazo solution.

As coupling components there come quite generally into consideration allproducts which have been recommended for the production of insolubleazo-dyestuils, for example B-naphthol, the arylides ofp-hydroxynaphthoic acid and the derivatives thereof capable of beingcoupled in l-position, the arylides of other acids, such as those of thehydroxycarbazol, hydroxyphenanthrene, hydroxydiphenylamine, andhydroxyanthracene carboxylic acids, coupling components with the CHzCOgroup, such as pyrazolone, acetoacetic derivatives, such as, forexample, the arylides from acetoacetic acid, bases of the'diphenylseries, such as benzidine, tolidine and dianisidine, further 1hydroxynaphthalene 4 arylketones, arylides of phenol carboxylic acids,such as arylides of the p-kresotinic acid or of xylenol carboxylic acidscapable of being coupled, etc.

As suitable diazotizable amines there may be mentioned the unsulionatedaromatic diazo-compounds which have also been recommended for theproduction of insoluble dyestuffs on the fiber, for example aniline,chloroand nitroanilines, chloro, nitroand chloronitrotoluidines,monoacylated p-, 0-, and m-phenylenediamines, aminodiarylethers,aminodiphenylamines, 04- and B-naphthylamines, aminoanthraquinones,aminocarbazoles, aminoazo-compounds, etc.

It has further been found that in an analogous manner colored reservesmay be produced under azodyestufis by incorporating dyestuffs into thereserve containing xanthogenate, which dyestuffs are then fixed on thefabric without influencing the reserving effect of the xanthogenate inany Way.

As salts of the xanthogenic acid there are preferably used the alkalimetal salts, but also other salts, for example heavy metal salts, suchas tin or zinc, or other metal salts, such as magnesium or aluminiumsalts.' Such salts are preferably formed in the printing color byconversion of the alkali xanthogenates with salts of other metals.

For producing colored reservations, dyestuffs (this term including leucocompounds of vat dyestuffs) which are capable of fixing on the goods areadded to the printing paste containing the salt of the xanthogenic acid,and printed.

For producing colored reservations basic dyestuffs and vat dyestuffs areparticularly suitable, the latter may also be applied in the form oftheir leuco compounds, this expression including the leuco derivatives,the leuco ester salts, the leuco ethers (of. British Patent No. 291,768)etc., re spectively. The leuco compounds, after combination of thecoupling component with the diazotized amine, are then transformed inthe usual manner into the corresponding dyestufis.

The following examples illustrate some methods of realization of thepresent invention, it being obvious that numerous other possibilitiesare possible still, the feature of the invention being, as alreadymentioned, the local destruction of the diazo compound on the fiber, dueto the presence of thesalts of the xanthogenic acid, it being inter aliairrelevant in which manner the colored eiiects, if any, are produced atthe reserved places:-

Example 1 125 g. of a solution of gum 1:1

50 g. of potassium xanthogenate 50 com. of water The goods are thendried again, and developed in the solution of a diaz'o-salt from4-chlor-2- aminodiphenyl ether. White effects on a red ground are thusobtained.

Example 2 The goods are then developed in a diazo solution containingper liter 12 g. of diazotized 4-nitrc- 3:6-diznethyl-1-aminoloenzene,and immediately afterwards passed through a bath of 5 g. of sodiumnitrite 20 00111. of hydrochloric acid of 22 B., adjusted to 1000 com.of water 7 Blue effects on a red ground are thus obtained.

Example 3 The fabric is prepared with 15 g. ofbenzoyl-lehydroxynaphthalene 15 com. of caustic soda solution of 36 B.

15 com. of Turkeyred oil of 50 per cent. strength 300 com. of boilingwater, adjusted to com. and then printed with a printing color preparedas follows 135 g. of gum 1:1 12.5 g. or Ciba blue 2131) paste (Schultz,Leipzig 12.5 g. of potash, and

10 g. of concentrated hydrosulfite powder are heated together untilreduction has taken place, cooled down and 50 g. of potassiumxanthogenate added The material is then steamed for 3 to 4 minutes inthe quick steamer and developed in a solution containing per liter 60 g.of a diazo-salt from 4- chloro-Z-aminodiphenyl ether, (corresponding to12 grams of 1-chloro-2-aminodiphenyl ether per liter). Blue effects on ared ground are thus obtained.

Example 4 The fabric is impregnated with a solution of 12 g. of2z3-hydroxynaphthoic acid anilide 18 com. of caustic soda solution of 36B. com. of Turkey'red oilof 50 per cent strength 300 com. of hot water12 g. of Katanol O, (of. Dr. P. Heermann, Technologie derTextilveredlung, Berlin v1926, page 164) adjusted to 1000 com.

and the dried fabric is printed with 2.5 g. of Methylene blue D(Schultz, Leipzig 1931. No. 1038) 5 com. or alcohol 45 com. of water 125g. of gum 1:1

50 g. of potassium xanthogenate. The material is then developed in asolution contaning per liter 50 g. of a diazo-salt from4-chloro-2-aminodiphenyl ether (corresponding to 10 grams of4-chloro-2-aminodiphenyl ether per liter) followed by washing andsoaping. Blue effects on a red ground are thus obtained.

of meta-nitro-p-toluidine per liter).

Example 5 The fabric is impregnated with the following solution:

g. of di-acetoacetic tolidide 20 com. of caustic soda solution of 38 B.20 com. of Turkey red oil of 50 percent strength,

adjusted to 1000 com.

The material is then printed with the resist prepared as per Example 1,and developed in a bath containing per liter '75 g. of a diazopreparation from m-nitroep-toluidine (corresponding to 15 g.

White effects on a yellow ground are thus obtained.

Example 6 The fabric is impregnated as indicated in Example 1 with 12 g.of 2: 3-hydroxynaphthoic acid anilide, and then printed with thefollowing resist:

125 g. of gum 1:1

50 g. of potassium xanthogenate 40 g. of stannous chloride com. ofwater. 1

The fabric is impregnated with 15 g. of the product known in the tradeby the name Naphthol ASLB (cf. Textile Colorist, 1931, page 561),printed with the resist prepared according to Example 6, and developedin a diazo -bath containing per liter 12 g. of the diazo-compound ofS-nitroo-anisidine. White effects on a brown ground are thus obtained.

What I claim is:-

1. Process for the production of reserves under azo-dyestuffs which areobtained by treating with diazo-compounds goods prepared with couplingcomponents, consisting in printing the goods with a metal salt ofXanthogenic acid prior to the treatment with the diazo-compound.

2. Process for the production of reserves under azo-dyestufis which areobtained by treating with diazo-compounds goods prepared with couwithdiazo-compounds goodsv prepared with coupling, components, consisting inprinting the goods prepared with they coupling component with a metal,salt of xanthogenic acid prior tov the treatment with thediazo-compound.

4. Process for the production of reserves under azo-dyestuffs which are.obtained by treating with diazo-compounds goods prepared with couplingcomponents, consisting in printing the goodsprepared with the couplingcomponent withan alkali metal salt of xanthogenic acid prior to thetreatment-with the diazo-compound.

5. Processv for the production of reserves under azo-dyestuffs which areobtained by treating with diazo-compounds goods prepared with couplingcomponents, consisting inprinting the goods with a salt of Xanthogenicacid together with a dyestuff which is capable of fixing on the goods,prior to. the treatment withthe diazo-compounds.

6. Process for the production of reserves under 1 azo-dyestufis whichare obtained by treating with diazo-compounds goods prepared withcoupling components, consisting in printing the goods with an alkalimetal salt of Xanthogenic acid together with a dyestufi which is capableof fixing on the goods, prior to the treatment with the diazocompound.

7. Process for the production of reserves under axe-dyestuffs which areobtained by treating with diam-compounds goods prepared with couplingcomponents, consisting in printing the goods With a salt of Xanthogenicacid together with a leuco-

